CN101418117A - Aromatic polycarbonate resin composite - Google Patents

Aromatic polycarbonate resin composite Download PDF

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CN101418117A
CN101418117A CNA2007101679448A CN200710167944A CN101418117A CN 101418117 A CN101418117 A CN 101418117A CN A2007101679448 A CNA2007101679448 A CN A2007101679448A CN 200710167944 A CN200710167944 A CN 200710167944A CN 101418117 A CN101418117 A CN 101418117A
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phenyl
mica
resin combination
resin
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CN101418117B (en
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中川秀则
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Teijin Ltd
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Teijin Chemicals Ltd
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Abstract

The present invention provides a resin composition, which contains 100 weight portions of aromatic panlite (A component), and 10 to 50 weight portions of mica (B component)which is measured by microtrac laser diffractometry, and has average particle diameter of between 10 and 100 mu m and less than 3 percent of number ratio of the particle size smaller than 10 mu m; and preferably, the resin composition also can contains 0.001 to 1 weight portion of organic sulfonic acid alkali (soil type) metal salt (C component), and 0.01 to 1 weight portion of fluoric antidripping agent (D component). For the mica, the number ratio of the particle size smaller than 7 mu m is preferably less than 1 percent; further, the number ratio of the particle size smaller than 5 mu m is less than 0.1 percent; and further, muscovite is obtained by a wet grinding method. The resin composition is particularly suitable for OA machine formed product. Even if organohalogens series fire retardants or phosphate series fire retardants are not contained, the provided resin composition also has good fire retardance, and excellent rigidity, heat resistance and thermostability in high temperature molding.

Description

Aromatic copolycarbonate resin composition
Technical field
The present invention relates to contain the resin combination and the moulding product thereof of aromatic copolycarbonate.Be substantially free of organic halogen flame retardant and the phosphoric acid ester flame retardant also has excellent flame-retardant performance even if relate in more detail, and the flame retardant resin composition and the moulding product thereof, particularly OA machine of the excellent heat stability when rigidity, thermotolerance and high-temperature molding.
Background technology
Aromatic polycarbonate resin has excellent mechanical characteristics, dimensional precision, electrical characteristic etc., is widely used in various fields such as electric and electronic field, automotive field, OA field of machines as engineering plastics.And in these purposes, for OA field of machines, electric and electronic field, in general, resin material needs flame retardant resistance.
In addition, in order to improve the rigidity of aromatic carbonate resin, cooperate inorganic filling materials such as glass fibre, carbon fiber, mica or talcum.At this moment, when at high temperature carrying out melt-processed with injection moulding machine, the decomposition owing to the caused aromatic polycarbonate resin of inorganic filling material can take place, thermostability becomes problem.And, the tendency that the thermal discharge that OA machine in recent years also has high performance to be caused increases, the required thermotolerance of material also increases.
In order to comply with the demand of flame retardant resistance, use the fire resistant aromatic makrolan resin (with reference to non-patent literature 1) that is mixed with organic halogen flame retardant, phosphoric acid ester flame retardant widely.But, even if in any of organic halogen flame retardant and phosphoric acid ester flame retardant, be mixed with the resin combination of this fire retardant in case when discarding, the influence of environment is become problem sometimes through burning or during burning disposal (thermal cycling) or by landfill.These fire retardants except these the query aspect the environment, have the alternate of being difficult to characteristic respectively, therefore can not easily replace.But, use other characteristic to supply, do not use basically the movement of the flame retardant resin material of these fire retardants also day by day to increase by product design etc.
As the improvement of thermostability, known have contain aromatic polycarbonate resin and have the inorganic filler of reactive behavior, specific Resins, epoxy or the resin combination (with reference to patent documentation 1) of phenoxy resin and specific silane coupling agent with respect to aromatic polycarbonate resin.But in the document, the concrete grammar of flame retardant resistance is not given in record.
Proposed in packing material, to have cooperated the composition of organo phosphorous compounds before.For example, known have a resin combination (with reference to patent documentation 2) that contains thermoplastic resin (aromatic polycarbonate resin, polyphenylene oxide resin, amorphism poly-allylat resin), organo phosphorous compounds, tabular packing material (mica, talcum), fibrous packing material.Known have the aromatic polycarbonate resin of containing, rubber modified styrene series resin, organo phosphorous compounds oligomer, fluoropolymer, a steatitic flame retardant resin composition (with reference to patent documentation 3).
But, cooperated the thermotolerance of composition of these organo phosphorous compoundss low, in addition, the rigidity when using talcum as packing material is insufficient.
Therefore, any in order to satisfy rigidity, thermotolerance, flame retardant resistance fully, essential further improvement.
(non-patent literature 1) " polycarbonate resin handbook " (～143 page of 5 row of 141 page of 6 row) (distribution of this single-minded volume, Nikkan Kogyo Shimbun, 1992)
No. 3495169 communique of (patent documentation 1) Japanese Patent
(patent documentation 2) TOHKEMY 2003-41131 communique
(patent documentation 3) TOHKEMY 2003-41112 communique
Summary of the invention
Even if the object of the present invention is to provide and be substantially free of organic halogen flame retardant, the phosphoric acid ester flame retardant also has excellent flame-retardant performance, and the resin combination of the excellent heat stability when rigidity, thermotolerance and high-temperature molding.
The inventor furthers investigate in order to reach above-mentioned purpose, found that by in the micaceous size-grade distribution of in the invention of above-mentioned patent documentation 1～3, fully not inquiring into, the number ratio of particle that makes median size and small particle size is in specified range, thermostability in the time of can taking into account rigidity, thermotolerance, high-temperature molding is further studied and has been finished the present invention.
The median size that the present invention contains aromatic polycarbonate resin (A composition) 100 weight parts and utilizes Mai Qike (マ イ Network ロ ト ラ Star Network) laser diffractometry to measure for (1) is that 10 μ m～100 μ m and the following particle number ratio of particle diameter 10 μ m are the resin combination of mica (B composition) 10～50 weight parts below 3%.
Among the present invention, so-called Mai Qike laser diffractometry is meant the scattered light of utilization by obtaining to particle-irradiation laser, tries to achieve the method for size-grade distribution.No matter dry type still is a wet type all can be measured, and utilizes the mensuration of wet type among the present invention.In addition, use volume average particle size as median size.The number of the particle that so-called particle diameter x μ m is following is represented as the ratio below the x μ m in the size distribution of the measurement result of Mai Qike laser diffractometry.Illustrated that determination object of the present invention is the scope of particle diameter 0.1 μ m～700 μ m.
By this formation (1), provide the resin combination of the excellent heat stability when having excellent rigidity, thermotolerance and high-temperature molding.
One of optimal way of the present invention is the resin combination of (2) above-mentioned formation (1), wherein with respect to total amount 100 weight parts of A composition and B composition, contains 0.001～1 weight part organic sulfonic acid alkali (great soil group) metal-salt (C composition).
One of optimal way of the present invention is the resin combination of (3) above-mentioned formation (1) or (2), wherein with respect to total amount 100 weight parts of A composition and B composition, contains the fluorine-containing Antidrip agent of 0.01～1 weight part (D composition).
Especially in OA molding machine product, require the situation of V-0 grade of testing vertical flammability of UL standard 94 a lot.In order to reach this V-0 grade, must prevent fusion drippage (drip and drop down), the representative illustration during this prevents have polycarbonate resin molecular weight raising, branched polycarbonate resin or ultra high molecular-weight polycarbonate resin cooperation and cooperate the Antidrip agent prescriptions such as (fluorine-containing Antidrip agents) that contains fluoropolymer.But, wherein the flame retardant resistance that synergy caused of performance C composition and to the forming process influence of resin combination very little aspect, preferred especially fluorine-containing Antidrip agent.Therefore, by this formation (3), can be provided in the above-mentioned resin combination that has good flame-retardance when having kept forming process.
One of optimal way of the present invention is the aromatic copolycarbonate resin composition of (4) above-mentioned formation (1)～(3), and wherein the B composition is that the number ratio of the following particle of particle diameter 7 μ m is the mica below 1%.One of preferred mode is the aromatic copolycarbonate resin composition of (5) above-mentioned formation (1)～(4), and wherein the B composition is that the number ratio of the following particle of particle diameter 5 μ m is the mica below 0.1%.By this formation (4), (5), the resin combination that the thermostability in the time of can providing high-temperature molding is more excellent.
One of optimal way of the present invention is the resin combination of (6) above-mentioned formation (1)～(5), and wherein the B composition is the white mica that obtains by the case of wet attrition method.By this formation (6), can provide rigidity excellent especially resin combination.
One of optimal way of the present invention is that (7) are by the formed moulding product of the resin combination that constitutes (1)～(6), preferred OA molding machine product.As described in putting down in writing in the past, the present invention satisfies the particularly desired various characteristics of OA molding machine product, therefore by this formation (7), even if can provide comprise be substantially free of organic halogen flame retardant, the phosphoric acid ester flame retardant also has excellent flame-retardant performance, and the moulding product, particularly OA molding machine product of the resin combination of the excellent heat stability when rigidity, thermotolerance and high-temperature molding.
Embodiment
The inventor thinks that the best mode of the present invention is to have concentrated the mode of above-mentioned each important document preferable range, for example is recorded in its typical example among the following embodiment.Certainly, the present invention is not limited to these modes.
Below, further specify detailed content of the present invention.
(A composition: aromatic polycarbonate resin)
The aromatic polycarbonate resin that uses as the A composition among the present invention is the product that dihydric phenol and carbonate precursor reaction are obtained.As one of reaction method example, can enumerate the solid phase ester-interchange method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.
As dihydric phenol typical example as used herein, can enumerate quinhydrones, Resorcinol, 4,4 '-xenol, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane of 2-[common name dihydroxyphenyl propane (BPA)], 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) pentanes of 2-, 4,4 '-(to phenylene diisopropyl fork) bis-phenol, 4,4 '-(metaphenylene diisopropyl fork) bis-phenol, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, two (4-hydroxy phenyl) oxygen, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, two (4-hydroxy-3-methyl phenyl) thioether, 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc.Preferred dihydric phenol is two (4-hydroxy phenyl) alkane, and wherein from the viewpoint of shock-resistance, preferred especially dihydroxyphenyl propane is widely used.
Among the present invention,, can also use the special polycarbonate that utilizes other divalent phenol manufacturing as the A composition except general polycarbonate dihydroxyphenyl propane is the polycarbonate.
For example, as part or all of divalent phenol composition, used 4,4 '-(metaphenylene diisopropyl fork) bis-phenol (following abbreviate as sometimes " BPM "), 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane (following abbreviate as sometimes " Bis-TMC "), 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, the polycarbonate (homopolymer or multipolymer) of two (the 4-hydroxy-3-methyl phenyl) fluorenes (following abbreviate as sometimes " BCF ") of 9-are suitable for because the strict especially purposes of the requirement of dimensional change that suction causes or morphological stability.Divalent phenol beyond these BPA preferably uses above, preferred especially 10 moles more than the % of 5 moles of overall % of the divalent phenol composition that constitutes this polycarbonate.
When special, when requiring high rigidity and good hydrolytic resistance, the A composition that especially preferably constitutes resin combination is the copolymerization polycarbonate of following (1)～(3).
(1) in the 100 moles of % of divalent phenol composition that constitute this polycarbonate, BPM is that 20～80 moles of % (more preferably 40～75 moles of %, further preferred 45～65 moles of %) and BCF are the copolymerization polycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, further preferred 35～55 moles of %).
(2) in the 100 moles of % of divalent phenol composition that constitute this polycarbonate, BPA is that 10～95 moles of % (more preferably 50～90 moles of %, further preferred 60～85 moles of %) and BCF are the copolymerization polycarbonate of 5～90 moles of % (more preferably 10～50 moles of %, further preferred 15～40 moles of %).
(3) in the 100 moles of % of divalent phenol composition that constitute this polycarbonate, BPM is that 20～80 moles of % (more preferably 40～75 moles of %, further preferred 45～65 moles of %) and Bis-TMC are the copolymerization polycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, further preferred 35～55 moles of %).
These special polycarbonate can use separately, can also suitably mix more than 2 kinds and use.In addition, these materials can also mix the back use with bisphenol A polycarbonate commonly used.
For the method for making and the characteristic of these special polycarbonate, for example in Japanese kokai publication hei 6-172508 communique, Japanese kokai publication hei 8-27370 communique, TOHKEMY 2001-55435 communique and TOHKEMY 2002-117580 communique etc., be documented.
Illustrated, in above-mentioned various polycarbonate, adjust copolymerization composition etc. and make water-intake rate and Tg (glass transformation temperature) following ranges person, the low warpage properties after the good and moulding of the hydrolytic resistance of polymkeric substance itself is also very good, so preferred especially in requiring the field of morphological stability.
(i) water-intake rate be 0.05～0.15%, preferred 0.06～0.13%, and Tg is 120～180 ℃ polycarbonate, perhaps
(ii) Tg is 160～250 ℃, preferred 170～230 ℃, and water-intake rate is 0.10～0.30%, preferred 0.13～0.30%, further preferred 0.14～0.27% polycarbonate.
Here, the water-intake rate of polycarbonate is to use diameter 45mm, the discoideus test film of thickness 3.0mm, according to ISO62-1980, measures the value that is immersed in the moisture rate after 24 hours in 23 ℃ of water.In addition, Tg (glass transformation temperature) measures the value of trying to achieve by the differential scanning calorimetry (DSC) according to JIS K7121.
As carbonate precursor, use carbonyl halide, carbonic diester or haloformate etc., can enumerate the bishaloformate of phosgene, diphenyl carbonate or dihydric phenol etc. particularly.
When above-mentioned dihydric phenol and carbonate precursor being made aromatic polycarbonate resin, can also use catalyzer, terminal terminator as required, be used to prevent the antioxidant of dihydric phenol oxidation etc. by interfacial polymerization.In addition, aromatic polycarbonate resin of the present invention comprises with the branched polycarbonate resin of the multi-functional aromatics copolymerization more than the trifunctional, with the polyestercarbonate resin of two functionality carboxyl acid copolymers of aromatic series or aliphatics (comprising alicyclic), with the copolymerized panlite of two functionality alcohol (comprising alicyclic) copolymerization and with the polyestercarbonate resin of this two functionalities carboxylic acid with two functionality alcohol copolymerization.In addition, can also be the mixture more than 2 kinds that mixes the gained aromatic polycarbonate resin.
Branched polycarbonate resin is because the anti-drippage performance that can further improve resin combination of the present invention synergistically and had, therefore preferred its use.As the multi-functional aromatics more than the trifunctional used in this branched polycarbonate resin, can enumerate Phloroglucinol, Off ロ ロ グ Le シ De, 4,6-dimethyl-2,4,6-three (4-hydroxy diphenyl) heptene-2,2,4,6-trimethylammonium-2,4,6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, 2, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenols of 6-, 4-{4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, triphenols such as α-Er Jiajibianji phenol, four (4-hydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) ketone, 1,4-two (4,4-dihydroxyl trityl group) benzene, or trihemellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and these sour acyl chlorides etc., wherein preferred 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, preferred especially 1,1,1-three (4-hydroxy phenyl) ethane.
The ratio of multi-functional compounds in the branched polycarbonate resin is 0.001～1 mole of %, preferred 0.005～0.9 mole of %, more preferably 0.01～0.8 mole of %, preferred especially 0.05～0.4 mole of % in the aromatic polycarbonate resin total amount.In addition, particularly under the situation of melt transesterification process, producing branched structure sometimes as side reaction, for this branched structure amount, also preferably is above-mentioned scope in the aromatic polycarbonate resin total amount.Illustrated,, can be passed through for this branched structure amount 1H-NMR measures and obtains.
The preferred alpha, omega-dicarboxylic acid of aliphatic two functionality carboxylic acids.As aliphatic two functionality carboxylic acids, for example can preferably enumerate alicyclic dicarboxylic acids such as straight chain saturated aliphatic dicarboxylic acids such as sebacic acid, dodecanedioic acid, tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid and cyclohexane dicarboxylic acid.As two functionality alcohol, more preferably alicyclic diol for example can be enumerated cyclohexanedimethanol, cyclohexane diol and tristane dimethanol etc.
And then can also use polycarbonate-poly organo alkyl copolymer with the polyorganosiloxane units copolymerization.
Reaction formation as interfacial polymerization, melt transesterification process, the solid phase ester-interchange method of carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc. of the manufacture method of aromatic polycarbonate resin is an all known method in various documents and patent gazette etc.
For the details of reaction formation beyond above-mentioned, known in books and periodicals and patent gazette etc.
The viscosity-average molecular weight of aromatic polycarbonate resin (M) is not particularly limited, and is preferably 1 * 10 4～5 * 10 4, more preferably 1.4 * 10 4～3 * 10 4, more preferably 1.4 * 10 4～2.4 * 10 4
As viscosity-average molecular weight less than 1 * 10 4Aromatic polycarbonate resin, the situation of the shock-resistance that can't obtain in the practicality to be expected etc. is arranged, in addition owing to can not obtain anti-fully drippage ability, therefore aspect flame retardant resistance, also be easy to variation.On the other hand, surpass 5 * 10 from viscosity-average molecular weight 4The resin combination that obtains of aromatic polycarbonate resin because the flowability when injection molding is poor, so versatility is poor.
Said viscosity-average molecular weight at first uses ostwald's viscometer by obtaining specific viscosity (η at the solution that is dissolved with the 0.7g aromatic copolycarbonate under 20 ℃ in the 100ml methylene dichloride by following formula among the present invention Sp).
Specific viscosity (η Sp)=(t-t 0)/t 0
[t 0For methylene dichloride fall a second number, t is second number that falls of sample solution]
Specific viscosity (η by gained Sp) obtain viscosity-average molecular weight M by following formula.
η Sp/ c=[η]+0.45 * [η] 2C (wherein [η] is limiting viscosity)
[η]＝1.23×10 -4M 0.83
c＝0.7
In addition, the computing method of above-mentioned viscosity-average molecular weight also is applicable to resin combination of the present invention or by the mensuration of the viscosity-average molecular weight of the moulding product of this resin combination moulding.That is, these viscosity-average molecular weights are the specific viscosity (η that obtain under 20 ℃ from the solution that is dissolved with 0.7g moulding product in the 100ml methylene dichloride among the present invention Sp) be updated to the numerical value of trying to achieve in the above-mentioned formula.
(B composition: mica)
Mica is meant the crushed material of the silicate minerals that contains aluminium, potassium, magnesium, sodium, iron etc.White mica, phlogopite, biotite, fluorophlogopite (micanite) etc. are arranged in the mica.Can use any mica among the present invention.Phlogopite, biotite are compared with white mica, itself softness.In addition, phlogopite, biotite are compared with white mica, because volume contains Fe in the principal constituent, so the tone of itself blackout.And fluorophlogopite is the material that the OH base of natural phlogopite is substituted by F, and itself costliness is impracticable.Preferred white mica.In addition, comminuting method during as the manufacturing mica, have use the dry type comminuting method that Dry-crusher pulverizes the former stone of mica and use Dry-crusher with the former stone of mica carry out adding after the coarse reduction entry make dewater after slurry form utilizes wet crushing mill formally to pulverize, exsiccant case of wet attrition method, though the cost of dry type comminuting method is low and commonly used, but owing to it is difficult to mica is pulverized imperceptibly, so the preferred mica that uses by the case of wet attrition manufactured among the present invention.
The mica that uses among the present invention is that the median size of utilizing the Mai Qike laser diffractometry to measure is that the mica of 10 μ m～100 μ m, preferred median size are that 20 μ m～60 μ m, further preferred median size are the mica of 30 μ m～50 μ m.The micaceous median size is during less than 10 μ m, and is then insufficient for the inflexible improved effect, on the other hand, do not see that also inflexible improves even if surpass 100 μ m, and the reduction of physical strengths such as impact characteristics is also obvious, and is not preferred.And the mica that uses among the present invention is except median size is in above-mentioned scope, and the particle number ratio below the particle diameter 10 μ m that measure by the Mai Qike laser diffractometry is below 3%, be preferably below 2.5%, more preferably below 2.0%.And then the number ratio of the particle that particle diameter 7 μ m are following is below 1%, be preferably below 0.7%, more preferably below 0.5%.And the following particle number ratio of particle diameter 5 μ m is below 0.1%, be preferably below 0.05%, more preferably below 0.01%.The particle number ratio of small particle size is not in above-mentioned scope the time, and the thermostability of aromatic copolycarbonate reduces.
Illustrated that the Mai Qike laser diffractometry of Shi Yonging is following measuring method herein.That is, utilize scattered light, obtain the method for size-grade distribution by being obtained to particle-irradiation laser.No matter dry type still is a wet type all can be measured, and is the mensuration of utilizing wet type among the present invention.Determination object of the present invention is the scope of particle diameter 0.1 μ m～700 μ m, with volume average particle size as median size.Use day Mai Qike MT-3000 of machine dress (strain) production to measure among the present invention.
The mica of B composition of the present invention can also carry out surface treatment by various surface treatment agents such as silane coupling agent, high-grade aliphatic ester and waxes.
(C composition: organic sulfonic acid alkali (great soil group) metal-salt)
Can enumerate the metal-salt of perfluoro alkyl sulfonic acid and basic metal or alkaline-earth metal or the metal-salt of aromatic sulphonic acid and basic metal or alkali earth metal salt as the azochlorosulfonate acid alkali among the present invention (great soil group) metal-salt.
As the basic metal that constitutes metal-salt of the present invention, can enumerate lithium, sodium, potassium, rubidium and caesium, as alkaline-earth metal, for example can enumerate beryllium, magnesium, calcium, strontium and barium.More preferably basic metal.In this basic metal, when the requirement of the transparency is higher, rubidium that the preferred ion radius is bigger and caesium, on the contrary because they and be of little use and be difficult to and make with extra care, so result's disadvantageous situation that aspect cost, becomes.On the other hand, aspect transparent, disadvantageous situation is arranged on the contrary at lithium favourable aspect cost, the flame retardant resistance and the littler metal of sodium plasma radius.In view of such circumstances, can distinguish the basic metal that uses in the sulfonic acid alkali metal salts, the sulfonic acid potassium salt of the balance excellence of where face characteristic most preferably in office.Can also and with this sylvite with contain other alkali-metal sulfonic acid alkali metal salts.
Object lesson as perfluoro alkyl sulfonic acid alkali (great soil group) metal-salt, can enumerate trifluoromethanesulfonic acid potassium, perfluor fourth potassium sulfonate, the own potassium sulfonate of perfluor, perfluorooctane sulfonate potassium, five fluorine ethyl sulfonic acid sodium, perfluor fourth sodium sulfonate, perfluorooctane sulfonate sodium, trifluoromethanesulfonic acid lithium, perfluor fourth sulfonic acid lithium, perfluor sulfonic acid in heptan lithium, trifluoromethanesulfonic acid caesium, perfluor fourth sulfonic acid caesium, perfluorooctane sulfonate caesium, the own sulfonic acid caesium of perfluor, perfluor fourth sulfonic acid rubidium and the own sulfonic acid rubidium of perfluor etc., these materials can use separately a kind or and with more than 2 kinds the use.Here, the scope of the carbon number of perfluoroalkyl preferred 1～18, more preferably 1～10 scope, further preferred 1～8 scope.Wherein, preferred especially perfluor fourth potassium sulfonate.
The carbon number of aromatic sulphonic acid alkali (great soil group) metal-salt is 7～50, be preferably 7～40, as object lesson, for example can enumerate diphenylsulfide-4,4 '-disulfonic acid disodium, diphenylsulfide-4,4 '-disulfonic acid dipotassium, 5-sulfoisophthalic acid potassium, 5-sulfoisophthalic acid sodium, the many sodium of the many sulfonic acid of polyethylene terephthalate, 1-methoxynaphthalene-4-calcium sulphonate, 4-dodecylphenyl ether disulfonic acid disodium, poly-(2,6-dimethyl phenylate) the many sodium of many sulfonic acid, poly-(1, the 3-phenylate) the many sodium of many sulfonic acid, poly-(1, the 4-phenylate) the many sodium of many sulfonic acid, poly-(2,6-phenylbenzene phenylate) the many potassium of many sulfonic acid, poly-(2-fluoro-6-butyl phenylate) many sulfonic acid lithium, the potassium sulfonate of benzene sulfonate, benzene sulfonic acid sodium salt, the Phenylsulfonic acid strontium, Phenylsulfonic acid magnesium, to the benzene disulfonic acid dipotassium, naphthalene-2,6-disulfonic acid dipotassium, biphenyl-3,3 '-disulfonic acid calcium, sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid dipotassium, sulfobenzide-3,4 '-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone-4-sodium sulfonate, benzophenone-3,3 '-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, the thionaphthene sodium sulfonate, diphenyl sulfoxide-4-potassium sulfonate, the formaldehyde condensation products of the formaldehyde condensation products of sodium naphthalene sulfonate and anthracene sulfonic acid sodium etc.In these aromatic sulphonic acid alkali (great soil group) metal-salts, preferred especially sylvite.In these aromatic sulphonic acid alkali (great soil group) metal-salts, preferred sulfobenzide-3-potassium sulfonate and sulfobenzide-3,3 '-disulfonic acid dipotassium, especially preferably their mixture (weight ratio of the former with the latter is 15/85～30/70).
(D composition: fluorine-containing Antidrip agent)
Fluorine-containing Antidrip agent as the D composition, can enumerate and have the fluoropolymer that protofibril forms ability, as this polymkeric substance can enumerate tetrafluoroethylene, tetrafluoroethylene based copolymer (for example tetrafluoroethylene/hexafluoropropylene copolymer etc.), No. 4379910 disclosed partially fluorinated polymkeric substance of communique of United States Patent (USP), by fluoridizing polycarbonate resin that bis-phenol makes etc.Wherein, preferably polytetrafluoroethylene (below be sometimes referred to as PTFE).
Have the molecular weight that protofibril forms the PTFE of ability and have high molecular weight, show by external force effects such as shearing force with between the PTFE in conjunction with, become fibrous tendency.Its molecular weight is 1,000,000～1,000 ten thousand, more preferably 2,000,000～9,000,000 in the number-average molecular weight of being tried to achieve by standard specific gravity.This PTFE can also use the aqueous liquid dispersion form except solid shape.This has PTFE that protofibril forms ability in order to improve dispersiveness in resin, to obtain excellent flame-retardant performance and mechanical characteristics more, can also use the PTFE mixture with the mixed style of other resin.
Have the PTFE commercially available product that protofibril forms ability as this, for example can enumerate テ Off ロ Application (registered trademark) 6J that Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le (strain) produces, Port リ Off ロ Application MPA FA500 that ダ イ キ Application industry (strain) is produced and F-201L etc.As the commercially available product of the aqueous liquid dispersion of PTFE, can enumerate テ Off ロ Application (registered trademark) 30J that Off Le オ Application AD-1, AD-936 that rising sun ア イ シ-ア イ Off ロ ロ Port リ マ-ズ (strain) produces, Off Le オ Application D-1 that ダ イ キ Application industry (strain) is produced and D-2, Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le (strain) produce etc. and be representative.
PTFE as mixed style, can use the material that makes by the following method: (1) mixes the aqueous liquid dispersion of PTFE and the aqueous liquid dispersion or the solution of organic polymer carries out method (the Japanese kokai publication sho 60-258263 communique that co-precipitation obtains to be total to cohesion mixture, the method that Japanese kokai publication sho 63-154744 communique etc. is put down in writing), (2) mix the aqueous liquid dispersion of PTFE and the method (method that Japanese kokai publication hei 4-272957 communique is put down in writing) of exsiccant organic polymer particle, (3) mix aqueous liquid dispersion and the organic polymer particle solution of PTFE equably, from this mixture, remove method (the Japanese kokai publication hei 06-220210 communique of each medium simultaneously, the method that Japanese kokai publication hei 08-188653 communique etc. is put down in writing), (4) will in the aqueous liquid dispersion of PTFE, be formed with the method (method that Japanese kokai publication hei 9-95583 communique is put down in writing) of the monomer polymerization of organic polymer and (5) aqueous liquid dispersion of PTFE and organic polymer dispersion liquid will be mixed equably after, further in this mixed dispersion liquid with ethene base system monomer polymerization, obtain the method (method that Japanese kokai publication hei 11-29679 communique etc. is put down in writing) of mixture afterwards.As the PTFE commercially available product of these mixed styles, can enumerate " メ Block レ Application A3000 " (trade(brand)name) and GE ス ペ シ ヤ リ テ イ-ケ ミ カ Le ズ company production " BLENDEX B449 " (trade(brand)name) of Mitsubishi's レ イ ヨ Application (strain) production etc.
As the ratio of the PTFE of mixed style, in 100 weight %PTFE mixtures, PTFE is preferably 1～60 weight %, 5～55 weight % more preferably.When the ratio of PTFE is this scope, can reach the good dispersion of PTFE.
(about the proportion of composing of each composition)
The present invention is that the number ratio of the following particle of 10 μ m～100 μ m and particle diameter 10 μ m is mica (B composition) 10～50 weight parts below 3%, preferred 12～40 weight parts, the more preferably resin combination of 15～30 weight parts for the median size that contains aromatic polycarbonate resin (A composition) 100 weight parts and utilize the Mai Qike laser diffractometry to measure.
The B composition be with respect to total amount 100 weight parts of A composition and B composition for less than 10 weight parts the time, can not bring into play the effect of rigidity raising etc. fully, when surpassing 50 weight parts, the tendency that the thermostability when showing high-temperature molding reduces.In the preferable range of B composition, the thermostability in the time of can taking into account favorable rigidity and high-temperature molding with higher level.
The content of C composition is 0.001～1 weight part, is preferably 0.005～0.5 weight part, 0.01～0.1 weight part more preferably with respect to total amount 100 weight part of A composition and B composition.When less than 0.001 weight part, can't obtain excellent flame-retardant performance, surpassing the opposite flame retardant resistance of 1 weight part can reduce.
The content of D composition is preferably 0.01～1 weight part, more preferably 0.05～0.8 weight part, 0.1～0.6 weight part more preferably with respect to total amount 100 weight parts of A composition and B composition.In this scope, then can take into account sufficient fusion drippage and prevent effect and flow characteristics.Illustrated that above-mentioned D components in proportions shows the amount of clean fluorine-containing Antidrip agent, during for the PTFE of mixed style, is shown that clean PTFE measures.
(other additive)
(phosphorus is stablizer)
Among the present invention, in order to obtain to have the resin combination of better tone and stable flowability, can also according to circumstances contain phosphorus is stablizer.
As phosphorus is stablizer, for example can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester etc.
As bi-ester of phosphite, specifically can enumerate triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tridecyl phosphite, the tricresyl phosphite monooctyl ester, tricresyl phosphite (octadecyl) ester, phosphorous acid didecyl monophenyl, phosphorous acid dioctyl monophenyl, phosphorous acid di-isopropyl monophenyl, phosphorous acid monobutyl diphenyl ester, phosphorous acid list decyl diphenyl ester, phosphorous acid list octyl group diphenyl ester, phosphorous acid 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) monooctyl ester, tricresyl phosphite (diethyl phenyl) ester, tricresyl phosphite (diisopropyl phenyl) ester, tricresyl phosphite (di-n-butyl phenyl) ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2, the 6-di-tert-butyl-phenyl) ester, distearyl pentaerythrityl diphosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, dicyclohexyl pentaerythritol diphosphites etc.
Bi-ester of phosphite as other can also use the material that has ring texture with the dihydric phenols reaction.For example can enumerate phosphorous acid 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) ester, phosphorous acid 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) ester, phosphorous acid 2,2 '-methylene-bis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) ester, phosphorous acid 2,2 '-ethylenebis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) ester etc.
As phosphate compound, can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl tolyl phosphate, the adjacent biphenyl ester of di(2-ethylhexyl)phosphate phenyl list, tributoxyethyl phosphate, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.
As phosphinate compound, can enumerate four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenyl, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4,3 '-biphenyl, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-3,3 '-biphenyl, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,4 '-biphenyl, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,3 '-biphenyl, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-3,3 '-biphenyl, two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester etc., preferred four (di-tert-butyl-phenyl)-biphenyl, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2, the 4-di-tert-butyl-phenyl)-biphenyl two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite esters.This phosphinate compound preferably can have the bi-ester of phosphite of 2 above substituted aryls with abovementioned alkyl and use.
As phosphonate compound, can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester, phosphenylic acid dipropyl etc.
Above-mentioned phosphorus is that stablizer not only can use a kind, can also mix more than 2 kinds and use.At above-mentioned phosphorus is in the stablizer, also preferred bi-ester of phosphite or phosphinate compound.The phosphate compound that especially preferably cooperates the trimethyl phosphite 99 representative.And, when containing the liquid crystal polyester of F composition, preferably cooperate the dialkyl group pentaerythritol diphosphites of trialkyl phosphites such as tridecyl phosphite, tricresyl phosphite monooctyl ester, tricresyl phosphite (octadecyl) ester and distearyl pentaerythrityl diphosphite representative.By the cooperation of this phosphorous acid ester, suppressed liquid crystal polyester and the unwanted transesterification reaction of aromatic polycarbonate resin, brought into play the viscoelastic property that liquid crystal polyester had effectively, finish the flowability and the inflexible improvement of resin combination.
(hindered phenol is a stablizer)
Resin combination of the present invention is a stablizer by further containing hindered phenol, the tone variation when further bringing into play forming process for example or long-term between the inhibition effect of the tone variation used etc.As hindered phenol is stablizer; for example can enumerate alpha-tocopherol; butylhydroxy toluene; sinapyl alcohol; vitamin-E; just-octadecyl-β-(4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester; the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 2; 6-di-t-butyl-4-(N; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-dimethylene two (6-α-Jia Jibianji-p-cresol); 2; 2 '-ethylenebis (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene two (4-methyl-6-tert butyl phenol); 4; 4 '-butylidene-bis(3-methyl-6-t-butyl phenol); triglycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; the 6-hexylene glycol is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [the 2-tertiary butyl-4-methyl 6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 4; 4 '-thiobis (6-tertiary butyl meta-cresol); 4; 4 '-thiobis (3 methy 6 tert butyl phenol); 2; 2 '-thiobis (4-methyl-6-tert butyl phenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) thioether; 4; 4 '-two-thiobis (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-three-thiobis (2; the 6-DI-tert-butylphenol compounds); 2; 2-sulfo-di ethylene bis-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2; two (n-octyl sulphur)-6-(the 4-hydroxyls-3 ' of 4-; 5 '-di-tert-butyl amido)-1; 3; the 5-triazine; N; N '-hexa-methylene two-(3; 5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; [3-(3 for N '-two; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2; 4; 6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester; three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester; 1; 3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanuric acid ester; 1; 3; 5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] ethyl isocyanuric acid ester and four [methylene radical-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.These materials all can easily obtain.Above-mentioned hindered phenol is that stablizer can use separately, can also make up more than 2 kinds and use.
Phosphorus is that stablizer and hindered phenol are total amount 100 weight parts of the use level of stablizer with respect to aromatic polycarbonate resin (A composition) and mica (B composition), is 0.0001～1 weight part, is preferably 0.001～0.5 weight part, 0.005～0.3 weight part more preferably.When stablizer is more very few than above-mentioned scope, be difficult to obtain the satisfactory stability effect, when too much, cause sometimes that then the rerum natura of composition reduces above above-mentioned scope.
(UV light absorber)
Resin combination of the present invention is because therefore its color harmony outward appearance excellence need not implement i.e. use such as covering with paint sometimes.Sometimes require good photostabilization under this situation, the cooperation of UV light absorber has effect under this situation.
As UV light absorber; specifically in benzophenone series; for example can enumerate 2; the 4-dihydroxy benaophenonel; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-4-octyloxy benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; 2-hydroxyl-4-methoxyl group-5-sulfoxide group (ス Le ホ キ シ) benzophenone; 2-hydroxyl-4-methoxyl group-5-sulfoxide group three (gibbsite) (ス Le ホ キ シ ト リ Ha イ De レ イ ト) benzophenone; 2; 2 '-dihydroxyl-4-methoxy benzophenone; 2; 2 '; 4; 4 '-tetrahydroxybenzophenone; 2; 2 '-dihydroxyl-4; 4 '-dimethoxy-benzophenone; 2; 2 '-dihydroxyl-4,4 '-dimethoxy-5-sodium diphenylsulfone ketone; two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane; 2-hydroxyl-4-dodecyl oxygen base benzophenone and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.
As UV light absorber, specifically in benzotriazole system, for example can enumerate 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole base phenyl), 2,2 '-TOPOT 2,2 (1,3-benzoxazine-4-ketone), 2-[2-hydroxyl-3-(3,4,5,6-tetrahydric phthalimide ylmethyl)-the 5-aminomethyl phenyl] benzotriazole, and 2-(2 '-hydroxy-5-methyl base acryloxy ethylphenyl)-2H-benzotriazole with can with the monomeric multipolymer of ethene base system of this monomer copolymerization, 2-(2 '-hydroxyl-5-acryloxy ethylphenyl)-2H-benzotriazole and the polymkeric substance etc. that can have 2-hydroxy phenyl-2H-benzotriazole skeleton with the monomeric multipolymer of ethene base system of this monomer copolymerization etc.
UV light absorber specifically in hydroxyphenyltriazinuv system, for example can enumerate 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and 5-hexyloxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and 5-methoxyphenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and 5-thanatol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and 5-propoxy-phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-butoxy phenol etc.The phenyl that can also enumerate 2-(4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-)-above-mentioned example compound such as 5-hexyloxy phenol is 2, the compound of 4-3,5-dimethylphenyl.
UV light absorber specifically in cyclic imide acid esters system, for example can enumerate 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-metaphenylene two (3,1-benzoxazine-4-ketone) and 2,2 '-p, p '-diphenylene two (3,1-benzoxazine-4-ketone) etc.
As UV light absorber; specifically in cyanoacrylate system; for example can enumerate 1; 3-pair-[(2 '-cyano group-3 '; 3 '-diphenylprop enoyl-) oxygen base]-2, two [(2-cyano group-3, the 3-diphenylprop enoyl-) oxygen base] methyl of 2-) propane, 1; 3-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen base] benzene etc.
Above-mentioned UV light absorber can also be by becoming the structure of monomeric compound that can radical polymerization, with the polymer-type UV light absorber of monomer copolymerizations such as this ultraviolet-absorbing monomer and/or light stability monomer and (methyl) alkyl acrylate.As above-mentioned ultraviolet-absorbing monomer, can preferably enumerate the compound that in the ester substituting group of (methyl) acrylate, contains benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imide acid esters skeleton and cyanoacrylate skeleton.
The use level of UV light absorber is with respect to total amount 100 weight parts of aromatic polycarbonate resin (A composition) and mica (B composition), is 0.01～2 weight part, is preferably 0.03～2 weight part, more preferably 0.02～1 weight part, 0.05～0.5 weight part more preferably.
(photostabilizer)
In resin combination of the present invention, can also and use photostabilizer with UV light absorber.As this photostabilizer, for example can enumerate two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, it is poly-that { [6-(1,1,3, the 3-tetramethyl butyl) amino-1,3,5-triazine-2,4-two bases] [(2,2,6, the 6-tetramethyl-piperidyl) imino-] hexa-methylene [(2,2,6,6-tetramethyl-piperidyl) imino-] } and poly-methyl-propyl 3-oxygen-[4-(2,2,6,6-tetramethyl-) piperidyl] hindered amine of representative such as siloxanes is photostabilizer.Above-mentioned photostabilizer can use separately, can also use the mixture more than 2 kinds.The combined amount of photostabilizer is with respect to total amount 100 weight parts of aromatic polycarbonate resin (A composition) and mica (B composition), is 0.0005～3 weight part, is preferably 0.01～2 weight part, 0.02～1 weight part more preferably.
(white dyes)
Resin combination of the present invention has the situation that must regulate tone.Under this situation, cooperate white dyes to have effect.As white dyes, can enumerate coumarin series, naphthalimide system, benzoxazole base system white dyes etc., wherein preferred coumarin series white dyes for example can preferably be enumerated Ha Star コ-Le ケ ミ カ Le (strain) as this white dyes and produce Ha Star コ-Le PSR.The use level of white dyes is with respect to total amount 100 weight parts of polycarbonate resin (A composition) and mica (B composition), be 0.0001～3 weight part, be preferably 0.0005～1 weight part, more preferably 0.0005～0.5 weight part, more preferably 0.001～0.5 weight part, be preferably 0.001～0.1 weight part especially.
(other fire retardant)
Even if resin combination of the present invention is substantially free of organic halogen flame retardant or the phosphoric acid ester flame retardant has also been reached excellent flame-retardant performance, even if cooperate above-mentioned fire retardant also can not hinder its flame retardant effect.But in order further to bring into play feature of the present invention, resin combination of the present invention preferably is substantially free of organic halogen flame retardant or phosphoric acid ester flame retardant.On the other hand, in order to bring into play feature of the present invention, further to improve flame retardant resistance, for example can also further cooperate siloxane-based fire retardant or various organic bases (great soil group) metal-salt.
This siloxane-based fire retardant is that compound, the chemical reaction when passing through burning with siloxane bond improve flame retardant resistance, can use all cpds that fire retardant proposed as aromatic polycarbonate resin.Silicone compounds by when it burns itself in conjunction with or combine, form structure with the composition that comes from resin, the reduction reaction when perhaps forming by this structure is given the polycarbonate resin flame retardant effect.Therefore, preferably contain the active high group in this reaction, more particularly, preferably contain at least a kind the group that is selected from alkoxyl group and hydrogen base (being the Si-H yl) of specified amount.Proportional as containing of this group (alkoxyl group, Si-H yl), be preferably 0.1～1.2mol/100g scope, more preferably scope, the scope of 0.15～0.6mol/100g more preferably of 0.12～1mol/100g.This ratio is tried to achieve by caustic leaching process, the hydrogen that silicone compounds produced by analytical unit weight or the amount of alcohol.Illustrated that alkoxyl group is preferably the alkoxyl group of carbon number 1～4, preferred especially methoxyl group.
In general, the structure of silicone compounds constitutes by arbitrary combination 4 kinds of siloxane units shown below.That is,
The M unit: (CH 3) 3SiO 1/2, H (CH 3) 2SiO 1/2, H 2(CH 3) SiO 1/2, (CH 3) 2(CH 2=CH) SiO 1/2, (CH 3) 2(C 6H 5) SiO 1/2, (CH 3) (C 6H 5) (CH 2=CH) SiO 1/2Deng 1 functionality siloxane unit,
The D unit: (CH 3) 2SiO, H (CH 3) SiO, H 2SiO, H (C 6H 5) SiO, (CH 3) (CH 2=CH) SiO, (C 6H 5) 22 functionality siloxane units such as SiO,
The T unit: (CH 3) SiO 3/2, (C 3H 7) SiO 3/2, HSiO 3/2, (CH 2=CH) SiO 3/2, (C 6H 5) SiO 3/2Deng 3 functionality siloxane units,
The Q unit: SiO 24 shown functionality siloxane units.
The structure of the siloxane-based fire retardant of mentioning among the present invention specifically can be enumerated Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, DnTpQq as the signal formula.Wherein, the structure of preferred silicone compounds is MmDn, MmTp, MmDnTp, MmDnQq, and further preferred construction is MmDn or MmDnTp.
Here, the Coefficient m in the above-mentioned signal formula, n, p, q are for representing the integer more than 1 of each siloxane unit polymerization degree, and the coefficient summation in each signal formula is the mean polymerisation degree of silicone compounds.This mean polymerisation degree be preferably 3～150 scope, more preferably 3～80 scope, more preferably 3～60 scope, be preferably 4～40 scope especially.During for this preferable range, then excellent flame-retardant performance becomes more excellent.As described later, contain in the silicone compounds of specified amount aromatic group, the transparency is also excellent.In addition, when m, n, p, q were numerical value more than 2, this siloxane unit that has coefficient can be bonded hydrogen atom or the different siloxane unit more than 2 kinds of organic residue.
Siloxane-based fire retardant can have the straight chain shape, also can have branched structure.In addition, be bonded in organic residue on the Siliciumatom and be preferably carbon number 1～30, organic residue of 1～20 more preferably.As this organic residue, specifically, can enumerate alkyl such as methyl, ethyl, propyl group, butyl, hexyl, decyl, cycloalkyl such as cyclohexyl, aryl and aralkyl such as phenyl, tolyl.The more preferably alkyl of carbon number 1～8, thiazolinyl or aryl.As alkyl, the alkyl of carbon numbers 1～4 such as special preferable methyl, ethyl, propyl group.
Siloxane-based fire retardant contains aryl can provide preferred aspect flame retardant resistance and the more excellent resin combination of the transparency.Aromatic series base shown in the more preferably following general formula (1) contains proportional (aromatic series base unit weight) and is preferably 10～70 weight % (more preferably 15～60 weight %).
Figure A200710167944D00201
In the formula (1), X independently represents the organic residue of monovalence of OH base, carbon number 1～20 separately.N represents 0～5 integer.In formula (1), n 2 can adopt the X of different kind separately when above.
Siloxane-based fire retardant can also contain reactive group except above-mentioned Si-H base and alkoxyl group, as this reactive group, for example can enumerate amino, carboxyl, epoxy group(ing), vinyl, sulfydryl and methacryloxy etc.
As the silicone compounds that in siloxane-based fire retardant, has the Si-H base, preferably enumerate and contain the unitary at least a above silicone compounds of formation shown in following general formula (2) and (3).
Figure A200710167944D00211
(in formula (2) and the formula (3), Z 1～Z 3Independent separately, expression hydrogen atom, the organic residue of monovalence of carbon number 1～20 or the compound shown in the following general formula (4).α 1～α 3 is independent separately, expression 0 or 1.M1 represents the integer more than 0 or 1.M1 is that 2 repeating units when above can adopt mutually different separately a plurality of repeating units in the formula (2).)
Figure A200710167944D00212
(in the formula (4), Z 4～Z 8Independent separately, the organic residue of monovalence of expression hydrogen atom, carbon number 1～20.α 4～α 8 is independent separately, expression 0 or 1.M2 represents the integer more than 0 or 1.M2 is that 2 repeating units when above can adopt mutually different separately a plurality of repeating units in the formula (4).)
In siloxane-based fire retardant,, for example can enumerate at least a kind the compound that is selected from compound shown in following general formula (5) and the general formula (6) as silicone compounds with alkoxyl group.
Figure A200710167944D00221
(in the formula (5), β 1Expression vinyl, the alkyl of carbon number 1～6, the cycloalkyl of carbon number 3～6, the aryl and the aralkyl of carbon number 6～12.γ 1, γ 2, γ 3, γ 4, γ 5, γ 6The alkyl of expression carbon number 1～6 and the aryl of cycloalkyl and carbon number 6～12 and aralkyl, at least 1 group are aryl or aralkyl.δ 1, δ 2And δ 3The alkoxyl group of expression carbon number 1～4.)
Figure A200710167944D00222
(in the formula (6), β 2And β 3Expression vinyl, the alkyl of carbon number 1～6, the cycloalkyl of carbon number 3～6, the aryl and the aralkyl of carbon number 6～12.γ 7, γ 8, γ 9, γ 10, γ 11, γ 12, γ 13, γ 14The aryl of the alkyl of expression carbon number 1～6, the cycloalkyl of carbon number 3～6 and carbon number 6～12 and aralkyl, at least 1 group are aryl or aralkyl.δ 4, δ 5, δ 6, δ 7The alkoxyl group of expression carbon number 1～4.)
Siloxane-based fire retardant is with respect to total amount 100 weight parts of aromatic polycarbonate resin (A composition) and mica (B composition), is 0.01～5 weight part, is preferably 0.05～3 weight part, 0.08～2 weight part more preferably.
Equally, various organic basess (great soil group) metal-salt can also be engaged in the resin combination of the present invention.For example, can enumerate alkali (great soil group) metal-salt of sulfuric ester, particularly can enumerate alkali (great soil group) metal-salt of the sulfuric ester of monobasic and/or polyalcohols, as its object lesson, for example can enumerate single, two, three, four sulfuric esters of sulfuric ester, the tetramethylolmethane of methylsulfuric acid ester, ethylsulfuric acid ester, lauryl sulfate ester, hexadecyl hydrosulfate ester, polyoxyethylene alkyl phenyl ether, the sulfuric ester of lauric monoglyceride, the sulfuric ester of hexadecanoic acid direactive glyceride, sulfuric ester of glyceryl monostearate etc.As alkali (great soil group) metal-salt of these sulfuric esters, alkali (great soil group) metal-salt of preferred lauryl sulfate ester.
As other organic bases (great soil group) metal-salt; can enumerate alkali (great soil group) metal-salt of aromatic sulfonamide, for example can enumerate alkali (great soil group) metal-salt of asccharin, N-(right-the tolylsulfonyl-base)-tolysulfonyl imines, N-(N '-benzylamino carbonyl) sulfanilimide and N-(phenyl carboxyl) sulfanilimide etc.The cooperation ratio of these organic basess (great soil group) metal-salt is 0.001～1 weight part, 0.005～0.5 weight part more preferably with respect to total amount 100 weight parts of A composition and B composition.
(packing material)
In the resin combination of the present invention, in the scope of performance effect of the present invention, can also cooperate B composition various packing materials in addition as strengthening filler.For example, can enumerate lime carbonate, glass fibre, granulated glass sphere, the glass hollow ball, the glass grinding fiber, sheet glass, carbon fiber, carbon plate, the carbon pearl, the carbon milled fibre, graphite, the superfine carbon fiber of chemical vapour deposition (the fiber footpath is less than 0.1 μ m), (the fiber footpath is less than 0.1 μ m for carbon nanotube, hollow form), soccerballene, tinsel, steel fiber, the metallic coating glass fibre, the metallic coating carbon fiber, the metallic coating sheet glass, silicon-dioxide, metal oxide particle, metal-oxide fiber, the metal oxide hollow ball, and various whisker (potassium titanate crystal whiskers, aluminium borate whisker and basic magnesium sulfate etc.) etc.These strengthen filler can contain a kind, and also two or more kinds may be used contains.
(other resin or elastomerics)
In the resin combination of the present invention, in the scope of performance effect of the present invention, can also lack ratio ground and use other resin or elastomerics.
As this other resin, for example can enumerate vibrin such as polyethylene terephthalate, polybutylene terephthalate, resins such as polyolefin resines such as polyamide resin, polyimide resin, polyetherimide resin, urethane resin, silicone resin, polyphenylene oxide resin, polyphenylene sulfide, polysulfone resin, polyethylene, polypropylene, polystyrene resin, vinyl cyanide/styrol copolymer (AS resin), acrylonitrile/butadiene/styrene multipolymer (ABS resin), polymethacrylate resin, phenol resins, Resins, epoxy.
In addition, as elastomerics, for example can enumerate iso-butylene/synthetic polyisoprene, styrene/butadiene rubbers, ethylene/propylene rubber, acrylic elastomer, polyester based elastomers, polyamide-based elastomerics, as hud typed elastomeric MBS (methyl methacrylate/ス テ レ Application/divinyl) rubber, MAS (methyl methacrylate/vinyl cyanide/vinylbenzene) rubber etc.
In addition, in order to give the various functions of moulding product and to improve characteristic, can also in resin combination of the present invention, lack the known additives of ratio ground cooperation own.These additives then are common use level only otherwise damage purpose of the present invention.
As this additive, can enumerate antiseize paste (for example PTFE particle), tinting material (carbon black for example, pigment such as titanium oxide, dyestuff), light diffusing agent (vinylformic acid crosslinked particle for example, the silicon crosslinked particle, sheet glass as thin as a wafer, calcium carbonate particles), fluorescence dye, inorganic is fluor (for example with aluminate as female crystalline fluor), antistatic agent, crystallization nucleating agent, inorganic and organic antibacterial agent, photocatalyst is a stain control agent (micropartical titanium oxide for example, micropartical zinc oxide), free radical generating agent, infrared absorbent (hot line absorption agent) and photochromic agent etc.
(manufacturing of resin combination)
When making resin combination of the present invention, can adopt arbitrary method.For example can enumerate and use V-type mixing machine, Henschel mixer, power chemical devices, extrude pre-mixing device such as mixing machine respectively with A composition～D composition and after other composition mixes fully arbitrarily; according to circumstances granulate by extrusion granulator machine or material cake preformer etc.; utilize afterwards exhaust twin shaft mixing roll (Er Shaft Le-ダ-) the melting mixing machine of representative carries out melting mixing, and by the granular method of machines such as tablets press.
As the supply method of each composition to the melting mixing machine, can enumerate (i) with A composition～D composition and other composition be conducted to the method for melting mixing machine respectively independently, (ii) after a part of pre-mixing with A composition～D composition and other composition, with remaining composition be conducted to independently the method for melting mixing machine, (iii) utilize water or organic solvent diluting mixed C composition be conducted to the method for melting mixing machine, (iv) with after this diluted mixture thing and other composition pre-mixing, be conducted to the method for melting mixing machine etc.Illustrated, when in the composition that cooperates fluent meterial being arranged (for example above-mentioned (iii), (iv) in), in the supply of melting mixing machine, can used so-called fluid infusion apparatus or liquid appending apparatus.
As forcing machine, can preferably use the forcing machine of venting port with the volatilization gas degassing that can be produced with the moisture in the raw material, by the melting mixing resin.Preferably be provided for the moisture that will be produced or volatile gases are discharged to the forcing machine outside efficiently from venting port vacuum pump.In addition, can also impurity be removed from resin combination being used to remove the zone of sneaking into before the screen cloth of extruding impurities in raw materials etc. is arranged on extruding dies portion.As this screen cloth, can enumerate wire netting, net-changing device, sintered metal plates (disc filter etc.) etc.As the melting mixing machine, except biaxial extruder, can also enumerate Banbury, mixing roller, single shaft forcing machine, the multiple screw extruder more than 3 etc.
The resin of as above extruding directly cuts off and carries out granulating, utilizes tablets press that granulating is carried out in this wire rod cutting after perhaps forming wire rod.When carrying out granulating, when being necessary to reduce the influencing of outside dust etc., preferably purify the atmosphere around the forcing machine.The gained particle shape can adopt cylinder, corner post and general shape such as spherical, more preferably cylinder.The diameter of this cylinder is preferably 1～5mm, more preferably 1.5～4mm, 2～3.3mm more preferably.On the other hand, the length of cylinder is preferably 1～30mm, more preferably 2～5mm, 2.5～3.5mm more preferably.
(moulding product)
The moulding product that contain resin combination of the present invention can obtain this particle injection molding usually.In this injection molding, not only common forming method can be enumerated, coated and molded in injection compression molding, injection extrusion forming, air-auxiliary injection forming, foaming (comprising the method for injecting supercutical fluid), produced by insert molding, the mould, heat insulating mold moulding, heating cooling mould molding, two look moulding, sandwich injection moulding and ultra-high speed injection molding etc. rapidly can also be enumerated.In addition, moulding can be selected any of cold runner mode and hot runner mode.
By the present invention, the resin combination extrusion moulding can also be made shapes such as various special-shaped extrusion molding articles, sheet material, film.In addition, in the moulding of sheet material, film, can also use inflation method, rolling process, casting method etc.And, by implementing specific extension operation, can also be as Heat-shrinkable Tubes.In addition, can also make the moulding product by aromatic copolycarbonate resin composition of the present invention is rotated moulding or blow molding etc.
(surface treatment)
Can also carry out various surface treatments to moulding product of the present invention.As surface treatment, can carry out hard coat, hydrophobic oleophobic coating, hydrophilic coating, anti-static coating, ultraviolet radiation absorption coating, infrared ray absorption coating and metallization various surface treatments such as (evaporations etc.).As surface treatment method, except the coating of liquor, can also enumerate vapour deposition method, molten method and the plating method of penetrating.As vapour deposition method, can use any of physical vapor deposition and chemical vapor deposition method.As physical vapor deposition, can enumerate vacuum vapour deposition, sputtering method and ion plating method.As chemical vapor deposition (CVD) method, can enumerate hot CVD method, plasma CVD method and optical cvd method etc.
Moulding product of the present invention are suitable for the OA utensil.
Embodiment
Below enumerate embodiment and further describe, but the present invention is not limited thereto.Illustrated, as estimating the following project of implementing.
(i) rigidity (bending elastic modulus)
Measure bending elastic modulus (MPa) according to ISO178.Test film is shaped as length 80mm * width 10mm * thickness 4mm.
(ii) flame retardant resistance
Carry out the testing vertical flammability of UL standard 94 with thickness 1.5mm, estimate its grade.
(iii) thermotolerance (loading deflection deformation temperature)
According to ISO75 with the 1.80MPa loading measure loading deflection deformation temperature (℃).Test film is shaped as length 80mm * width 10mm * thickness 4mm.
(iv) thermostability (molecular weight reduction)
(Sumitomo heavy-duty machine tool industry (strain) is produced: SG-150U) under 80 ℃ of 310 ℃ of barrel temperatures, die temperature by injection moulding machine, in the moulding of the about 90g of weight that comprises 3 segment type plates (width 50mm, length 90mm, thickness are apart from watering oral-lateral 3mm (length 20mm), 2mm (length 45mm), 1mm (length 25mm)), carry out 10 minutes delay test, thereby observed molecular weight changes, the thermostability of evaluating resin composition.Moulding be by carry out 30 injections continuously shaped after, under the state that measures, barrel is retreated, under this state, kept 10 minutes, carry out that the method for moulding once more implements.The inner resin that 4 injection parts are arranged that is detained of barrel.Will be from particulate viscosity-average molecular weight (M 1) in deduct the viscosity-average molecular weight (M of the 2nd injection after be detained handling 2) poor (M 1-M 2) as the reduction amount (M) of molecular weight, be recorded in the table.
As raw material, use following material.
(A composition)
PC-1: by dihydroxyphenyl propane and as the tert.-butyl phenol of terminal terminator and phosgene by interface polycondensation synthetic straight chain shape aromatic polycarbonate resin powder (Supreme Being people changes into (strain) and produces: パ Application ラ イ ト L-1225WS, viscosity-average molecular weight 20,900)
PC-2: by dihydroxyphenyl propane and as the tert.-butyl phenol of terminal terminator and phosgene by interface polycondensation synthetic straight chain shape aromatic polycarbonate resin powder (Supreme Being people changes into (strain) and produces: パ Application ラ イ ト L-1225WX, viscosity-average molecular weight 19,700)
PC-3: by dihydroxyphenyl propane and as the tert.-butyl phenol of terminal terminator and phosgene by interface polycondensation synthetic straight chain shape aromatic polycarbonate resin powder (Supreme Being people changes into (strain) and produces: CM-1000, viscosity-average molecular weight 16,000)
(B composition)
SA410: median size: 45 μ m, below the particle diameter 10 μ m: 1.6%, below the particle diameter 7 μ m: 0.2%, below the particle diameter 5 μ m: (strain) mountain pass mica industry white mica of producing: SA-410 0%,
A21: median size: 25 μ m, below the particle diameter 10 μ m: 20%, below the particle diameter 7 μ m: 10%, below the particle diameter 5 μ m: (strain) mountain pass mica industry white mica of producing: A-21 4.3%,
A41: median size: 45 μ m, below the particle diameter 10 μ m: 3.5%, below the particle diameter 7 μ m: 1.3%, below the particle diameter 5 μ m: (strain) mountain pass mica industry white mica of producing: A-41 0.2%,
B82: median size: 155 μ m, below the particle diameter 10 μ m: 0.6%, below the particle diameter 7 μ m: 0%, below the particle diameter 5 μ m: (strain) mountain pass mica industry white mica of producing: B-82 0%,
(C composition)
Bayowet: the perfluor fourth sulfonic acid potassium salt of fluoride ion amount 40ppm (バ イ エ Le company produces BayowetC4)
KSS: sulfobenzide-3, the 2:8 mixture of the single disulfonic acid potassium salt of 3 '-disulfonic acid di-potassium and sulfobenzide-3-(コ-シ-PVC-ジ ヤ パ Application is produced KSS)
(D composition)
PTFE: have tetrafluoroethylene (ダ イ キ Application industry (strain) production: Port リ Off ロ Application MPA FA500) that protofibril forms ability
B449: contain and have protofibril and form the polytetrafluoroethylparticle particle of ability and the mixture (polytetrafluoroethylene content 50 weight %) of styrene-acrylonitrile copolymer particle (the GE ス ペ シ ヤ リ テ イ-production BLENDEXB449 of ケ ミ カ Le ズ company)
(other)
TMP: phosphorus is that stablizer (produce: TMP) by big eight chemical industry (strain)
SL: (reason is ground PVC ミ Application (strain) production to releasing agent: SL900)
Embodiment 1～5, comparative example 1～3
Roll the machine of mixing mixed aromatic polycarbonate resin, silicate minerals, sulfonic acid alkali metal salts and PTFE and other composition equably to form shown in the table 1 to use, make premixture.This mixture is supplied to the 1st supplying opening of the screw rod root of two forcing machines of exhaust [(strain) JSW produces TEX30XSST] that are positioned at diameter 30mm Φ, under 280 ℃ of barrel temperatures, screw rod revolution 150rpm, spray volume 20kg/h and exhaust decompression degree 3kPa, melt extrude, make particle.
At 120 ℃ of following particles by the dry gained of heated air circulation type drying machine 5 hours.After the drying, (Sumitomo heavy-duty machine tool industry (strain) is produced: SG-150U) at the test film of 310 ℃ of barrel temperatures, 80 ℃ of compacted under evaluations of die temperature usefulness, estimate respectively by injection moulding machine.
Figure A200710167944D00281
By above-mentioned table as can be known, resin combination of the present invention have other mica the superperformance that can't reach.
The effect of invention
Resin combination of the present invention is by making average grain diameter and granule in the size distribution of mica The particle number ratio in footpath is in particular range, thereby the heat when rigidity, heat resistance, high-temperature molding Excellent in stability. Resin combination of the present invention is owing to be used in combination organic sulfonic acid alkali (great soil group) gold Belong to salt or fluorine-containing Antidrip agent, and use as the preferred material of mica, so anti-flammability is also excellent Different. Resin combination of the present invention is in each of OA field of machines, electric and e-machine field etc. Extremely useful in the kind industrial use, satisfy especially the superperformance that is adapted to the OA machine. Exist especially PC, notebook computer, game machine (home-use game machine, professional with game machine, marble Dish and throw coin-freed apparatus etc.), display unit (CRT, liquid crystal, plasma, projector and organic EL etc.) and printer, duplicator, scanner and facsimile machine (compounding machine that comprises them) Deng in preferred.
Resin combination of the present invention is useful in the purposes that other haves a wide reach, and for example can enumerate Portable information end (so-called PDA), mobile phone, portable books (dictionary class etc.), portable Television set, recording medium (CD, MD, DVD, second generation high density compact disc, hard disk etc.) The reading device of driver, recording medium (IC-card, intelligent medium, memory stick etc.), optics shine Camera, digital camera, parabola antenna, electric tool, VTR, flatiron, hair-dryer, cook Device, micro-wave oven, sound machine, illumination machine, refrigerator, air-conditioning, air cleaner, anion Generator and typewriter etc. can also use in these parts to be formed by resin combination of the present invention Products formed. As other products formed, can enumerate lamp socket, lamp reflector, lampshade, instrument board, Centre panel, deflector parts, auto navigation parts, automobile audiovisual parts, automobile computer The vehicle parts such as parts. As known from the above, the industrial effect reached of the present invention is very big.

Claims (9)

1. resin combination, it contains aromatic polycarbonate resin (A composition) 100 weight parts and the median size measured by the Mai Qike laser diffractometry is that 10 μ m～100 μ m and the particle number ratio below the particle diameter 10 μ m are mica (B composition) 10～50 weight parts below 3%.
2. the described resin combination of claim 1 wherein, contains organic sulfonic acid alkali (great soil group) metal-salt (C composition) 0.001～1 weight part with respect to total amount 100 weight parts of A composition and B composition.
3. claim 1 or 2 described resin combinations wherein, contain fluorine-containing Antidrip agent (D composition) 0.01～1 weight part with respect to total amount 100 weight parts of A composition and B composition.
4. each described resin combination of claim 1～3, wherein the B composition is that the following particle number ratio of particle diameter 7 μ m is the mica below 1%.
5. each described resin combination of claim 1～4, wherein the B composition is that the following particle number ratio of particle diameter 5 μ m is the mica below 0.1%.
6. each described resin combination of claim 1～5, the wherein white mica of B composition for obtaining by the case of wet attrition method.
7. each described resin combination of claim 2～6, wherein the C composition is perfluoro alkyl sulfonic acid alkali (great soil group) metal-salt or aromatic sulphonic acid alkali (great soil group) metal-salt.
8. the moulding product that contain each described resin combination of claim 1～7.
9. described moulding product of claim 8, it is OA molding machine product.
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CN101792585A (en) * 2010-03-16 2010-08-04 广州市番禺区天宇塑料实业有限公司 Flame-retardant polycarbonate composition and preparation method thereof
CN101722697B (en) * 2008-10-29 2013-08-28 帝人化成株式会社 Resin shaping body
CN108137914A (en) * 2015-12-08 2018-06-08 日本A&L株式会社 Thermoplastic resin composition
CN111875943A (en) * 2020-08-07 2020-11-03 宁波耀众模塑科技有限公司 Carbon-containing high polymer material mixture for flame retardant for polyurethane foaming product

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JP3888759B2 (en) * 1998-01-12 2007-03-07 帝人化成株式会社 Antistatic resin composition having flame retardancy and molded article
JP4505088B2 (en) * 1999-11-18 2010-07-14 帝人化成株式会社 Aromatic polycarbonate resin composition
DE10061080A1 (en) * 2000-12-08 2002-06-13 Bayer Ag Polycarbonate compositions
JP2004331718A (en) * 2003-04-30 2004-11-25 Mitsubishi Engineering Plastics Corp Thermoplastic resin composition
CN100427545C (en) * 2006-07-27 2008-10-22 上海交通大学 Process for preparing polycarbonate /acrylonitirle-ternary ethyl propylene rubber-styrene resin / laminated silicate nano composite material

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CN101722697B (en) * 2008-10-29 2013-08-28 帝人化成株式会社 Resin shaping body
CN101792585A (en) * 2010-03-16 2010-08-04 广州市番禺区天宇塑料实业有限公司 Flame-retardant polycarbonate composition and preparation method thereof
CN108137914A (en) * 2015-12-08 2018-06-08 日本A&L株式会社 Thermoplastic resin composition
CN108137914B (en) * 2015-12-08 2022-09-09 日本A&L株式会社 Thermoplastic resin composition
CN111875943A (en) * 2020-08-07 2020-11-03 宁波耀众模塑科技有限公司 Carbon-containing high polymer material mixture for flame retardant for polyurethane foaming product

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